Absorption Spectra of Solids from Periodic Equation-of-Motion Coupled-Cluster Theory
Xiao Wang, Timothy C. Berkelbach
Abstract
We present ab initio absorption spectra of six three-dimensional semiconductors and insulators calculated using Gaussian-based periodic equation-of-motion coupled-cluster theory with single and double excitations (EOM-CCSD). The spectra are calculated efficiently by solving a system of linear equations at each frequency, giving access to an energy range of tens of electronvolts without explicit enumeration of excited states. We assess the impact of cost-saving approximations associated with Brillouin zone sampling, frozen orbitals, and the partitioned EOM-CCSD approximation. Although our most converged spectra exhibit line shapes that are in good agreement with experimental spectra, they are uniformly shifted to higher energies by about 1 eV, which is not explained by the remaining finite-size errors. We tentatively attribute this discrepancy to a combination of vibrational effects and the remaining electron correlation, i.e., triple excitations and above.